Vinylethylene carbonate and its



Patented June 20,1050

VINYLE'I'HYLENE CAIBONATI AND ITS PREPARATION Wlllhm W.

to E. I. du Pont de Nemonrs & 012%.,

mlngton. Del.,a corporation of Delaware NDra. tion 3,1

who? Hassle.

scum. (cl. see-ass) This invention relates to organic chemistry and more particularly to a new organic carbonate and to its preparation.

This invention has as an object the preparation of a new organic carbonate. A further object is the preparation of a new polymerisable compound. other oblects will appear hereinafter.

These objects are accomplished by vinylethylene carbonate of the probable formula qm-crn-cn-om \i and its preparation by carbon dioxide with butadiene monoxide, i. e.,

o on-on-om '5' I I at elevated temperatures, preferably in the range 176-325 C., in the presence of a solid base, preferably potassium hydroxide on activated charcoal vinylethylene carbonate, or 3-butene-l,2-dlol carbonate as it may also be called, is a colorless liquid boiling at approximately 101' C./5 mm. or at 123' C./14 mm. It ha a refractive index of a, 1.447 and a density of (14 1.183. On heatin; with bensoyl peroxide ,it polymerizes to a resin.

The following examples in which parts are by weight are illustrative of the invention.

Example I Apressurevesselwasfllledtoabout'hitscas pacity with-105 parts of butadiene monoxide. To I the vessel was then added 150 parts of carbon dioxide and parts of 10% potassium hydroxide deposited on activated charcoal (i. e., 10 parts H per parts carbon). The vessel was sealed and heated at 200 C. under autogenous pressure for eight hours. The vessel was then opened, the product was separated from the catalyst by nitration. and distilled. This gave 72 parts of a oolo'rlea liquid boiling at about 123 C. at 14 mm. 40

Other properties obtained were: a 1.4472 and is 1.1827. The following data indicate that this product is vinylethylene carbonate:

Carbon and hydrogen analyses of the product gave the following results: Calculated for 00300:: C. 52.04%; H, 5.30%. Found: C. 53.18%, 53.18%; H. 5.60%. 5.50%.-

On hydrolysis with aqueous sodium hydroxide the product yielded sodium carbonate. Titration sults'z Calculated for m: cc. case's.

Found: 00:, 87.70%.

on heating the product with 5% of bensoyl peroxide for nineteen hours at 78 C. a pale yel- 5 low resin was obtained. A further sample of the product, i. e., of the liquid boiling at 123' C./14 mm., was heated at 130 C. with 0.5% di-tertiarybutyl peroxide under 7500 atmospheres pressure. This gave a clear, brittle solid which softened 10 at about C. This solid was insoluble in water and in most organic solvents tested but was soluble in ethylene carbonate. The following analysis indicates that this solid is a polymer of vinylethylene carbonate: Analysis: Calculated 10 for polyvlnylethylene carbonate: [(CsHeO:)s]2.

C. 52.64%; H. 5.30%. Found: C. 52.92%. 52.97%; 5.71%. 5.57%.

Emmple II 20 Fifty parts of butadiene monoxide, 10 parts of 5% sodium hydroxlde-on-carbon, and 250 parts of carbon dioxide were charged into a shaker tube and'heated under autogenous pressure at 225 C. for eight hours. The reaction 5 mixture was separated from the catalyst and distilled, first at atmospheric pressure to remove unchanged butadiene monoxide (42.5 parts, boiling 05-07 0.), and then at reduced pressure to separate the vinylethylene carbonate. The carbonate (0.5 part) was identified by treatment with cold sodium hydroxide in methanol which resulted in the precipitation of sodium carbonate. From the foregoing examples it is apparent that, although vinylethylene carbonate (CsHeOs) 5 is decomposed on treatment with alkali in aqueous or alcoholic solutions even in the cold. it can nevertheless be obtained in good yield at elevated temperatures from butadiene monoxide and carbon dioxide in the presence of solid potassium 40 hydroxide. Under the conditions used in preparing vinylethylene carbonate the potassium hydroxide reacts with carbon dioxide to form potassium bicarbonate. Hence it is to be understood that reference to potassium hydroxide in the claims includes its reaction product with carbon dioxide. Sodium hydroxide can also be used as catalyst but is much less effective. Other alkalies, e. g., lithium hydroxide, sodium carbonate, sodium bicarbonate and potassium cargo bonate, .also have some catalytic effect. The

catalyst; can be used alone but are preferably used on an inert support, such as carbon, pumice, alumina or silica gel. In examples I and 11 the reaction is carried out under autogenous presdthehydrolysisproductsgavethefollowingre-fl sure which, under the conditions used, was

- 3 roushlyof the orderof300 atm Higher or lower pr can be employed but it M deairable to operate above 30 atmospheres and preferably within the reuse of 100 to 3000 atmospheres. I

As illustrated in Example I, vinylethylene carbonate can be polymerized to resinous products when heated in the presence of a vinyl-type polymerization catalyst. such as an orsanic peroxide. In general. free-radical producing substances can be used as catalysts in the polymeriaation. Polymerization of vinylethylene car- 'honate in the presence of other pclymerizable unsaturated compounds leads to the formation of copolymers. As examples of polymerizable l6 materials with which vinylethylene carbonate can be copolymerized may be mentioned oleflns, e. an, ethylene, isobutylene and styrene; dienes. e. z., hutadiene and chloroprene; vinyl esters, e. 3.. vinyl chloride and vinyl acetate; ac ylic compounds. e. g., ethyl acrylate, 'acrylonitrile, and methyl methacrylate; fluoroethylenes. e. 3.. vinyl fluoride and tetrafluoroethylene; maleic and fumarlc compounds. e. 8., maleic anhydride and diethyl fumarate; and vinyl ethers, e. 3., vinyl ethyl ether and vinyl butyl ether. The polymers, including the copolymers, can be usedin making molding, coating and adhesive compositions 4 eneearhcnatewhereincarhondicaideandbutadienemonoaide,

arereactedatl'lm'aandunder l00to8000 atmospheres pressure in the presence of solid po- I tassium hydroxide.

Other uses for vinylethylene carbonate are as 30 solvents and as intermediates in the preparation of other compounds.

The foregoing detailed description has been given for clearness of understanding only and no unnecessary limitations are to be understood therefrom. The invention is not limited to the exact details shown and described for obvious I modifications will occur to those skilled in the What is claimed is:

l. Vinylethylene carbonate.

2. A process for the preparation of vinylethyl- 3. A process for the preparation of Methylene carbonate wherein carbondioxide and bu diene monoxide.

' cin-ou-on-om o reacted at 175-325 C. and under 100 to 3000 annospherespreasureinthepresenceofasolid alkali metal hydroxide.

4. A process for the preparation of vino wherein carbon dioxide and butadiene monoxid a own-ba-um are reacted at rill-225C. and a pressure of at least 80 atmospheres in the presence of a solid assurances 0mm The following references are of record in the ille of this patent: v srrs'rns ra'mn'rs Number Bissinz'er et al.. J. Am Chem. 800.. vol. co, Dec. 1941. mes 2955-2961. 

1. VINYLETHYLENE CARBONATE. 